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Effect of nanoparticle SiO2 grafted poly (methyl methacrylate) on poly(l-lactic) acid crystallization

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Abstract

For practical applications of poly(l-lactic acid) (PLLA), PLLA crystallization with keeping transparency is preferable. As one method to keep transparency without inhibiting crystallization, we prepared SiO2 nanoparticles which were modified with poly (methyl methacrylate) (PMMA-g-SiO2). FT-IR and TG–DTA measurement indicated that PMMA was grafted on SiO2 surface successfully. TG–DTA and GPC measurement of free PMMA cleaved from PMMA-g-SiO2 determined graft density of PMMA as 0.039 chains/nm2. The effect of PMMA-g-SiO2 on PLLA crystallization was characterized by DSC measurement and POM observation. Although PMMA-g-SiO2 could not promote PLLA crystallization significantly like commercial crystal nuclear agents, it did not inhibit PLLA crystallization. By UV measurement and Haze meter, it was indicated that crystallized PLLA with PMMA-g-SiO2 generated 3.5–5.3 times higher transparency than crystallized PLLA with/without commercial nucleating agent. TEM observation indicated that the aggregation size of PMMA-g-SiO2 was 21.7 ± 13.9 nm which was smaller than visible wavelength. Transparency improvement likely resulted from size-reduced aggregation of PMMA-g-SiO2 in PLLA matrix. On the other hand, PMMA-g-SiO2 made size of generated spherulite smaller but increased its number in PLLA matrix, which inhibited transparency improvement.

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Acknowledgments

The authors appreciated Nissan Chemical Industries, Ltd. for kind supply of silica nanoparticles used in this study. The authors also appreciated Dr. Takeshi HIGUCHI for his cooperation in TEM analyses.

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Author notes

  1. Tomoko Shirahase

    Present address: Graduate School of Science and Engineering, Tokyo Institute of Technology, 2-12-1-S8-43 Ookayama, Meguro-ku, Tokyo, 152-8550, Japan

  2. Moriya Kikuchi

    Present address: Department of Polymer Science and Engineering, Yamagata University, Yamagata, Japan

  3. Motoyasu Kobayashi

    Present address: Department of Applied Chemistry, Kogakuin University, Tokyo, Japan

Authors and Affiliations

  1. Institute for Materials Chemistry and Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan

    Tomoko Shirahase, Moriya Kikuchi, Motoyasu Kobayashi & Atsushi Takahara

  2. Science and Technology Agency, ERATO, Takahara Soft Interfaces Project, Fukuoka, Japan

    Moriya Kikuchi, Motoyasu Kobayashi & Atsushi Takahara

  3. Graduate School of Engineering, Kyushu University, Fukuoka, Japan

    Takamichi Shinohara & Atsushi Takahara

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  1. Tomoko Shirahase
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Correspondence to Tomoko Shirahase.

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Shirahase, T., Kikuchi, M., Shinohara, T. et al. Effect of nanoparticle SiO2 grafted poly (methyl methacrylate) on poly(l-lactic) acid crystallization. Polym. Bull. 72, 1247–1263 (2015). https://doi.org/10.1007/s00289-015-1336-1

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